Process of making camphene.



' -EsrrE s'rsTE's OTTO CHARLES BILLETER, or BASEL, SWITZERLAND, ASSIGNOR To THE lcosrom'rion or cHEMIcAL WORKS, FOEMERLY sANDoZ, or BASEL, SWITZERLAND.

rsoonss or MAKING celermente.'

Specification of Letters Patent.

retenes .runs 1e, isos.' i'

Application flied June 24, 19M. taril No. SEOBB.

To ali whom 'it may concern;

Be it known that i, OTTO CHARLEs'BILLE- TER, doctor of philosophy, chemist, end resident of 23 Rotoer erstrasse, BaseLSWitzer lcndistte invente new and useful improve inents in the Manufacture of Can1phene,.of

' which the following is e specification.

As# is known, pinene hydroclilorid is only incompletely decomposed b soda lye alone without the addition of a so Vent even when y the operation is conducted in the autoclave and at a hivh temperature. The hydrochloric acidis owevers lit OH quantitatively ,if the reectio'n is -pe ormed 1n a mediumv which Will-completely .or partly dissolve not only the saponifying agent but also the pineje hydrochlorid. Suitable solvents for "this purpose ere in particular Weak acids suolo as phenols, naphthols, acetic acid or stesric acid, these eveu sllowin bases such as oxitl ol zinc, copper or leed. Having in mind the property possessed by the higher alcohols and by the carbohydrates of largely dissolving lime to form strongly basic alcoholates and saccharates, l conceived the' idee lof em loying alkalics and soluble earth alkali derivatives for thepur- Y pose of ssponiiying pinene hydrochlorid, and found as s resut of experiment that pinene sodi-.tl e or Water and glycerin, inannitt, estrie, beet-sugar, glucose or starch.

During this operation the; solubleI 'carbony-k salt and is therefore s. very valuelole byproduct. This' 'formation of the scid requires a strong excess of alkali.

Example l. 340 arts of pinene hydrochloridy are mined Witv 34() parts of glycerin, 375 parts vof 33 soda lye and 100 parts of Water and are heated' in an autoclave for 12 yhours at i600 C. with constant stirring. l/Vhen.-

the reaction is linished the csznpliene free from chlorin is distilled with steam.

Example ll. NG parts of lime are con- Verted into lime Witter with 480 parts of Wstcr and are mixed with 345 parts of beet sugar. To the thick poste which is formed,

are further added 345 parts of pinene hydro-- of the` use of weairer i hydrochlorid con be readily converted into. csmpheneree from chlorin by, the ectiono.

Aresdilqy isolsited ss tlie free acid or as soluble @tutti and tte when is tested et time. an autoclave provided with c, stirrsr until the camphene which is formed proves to be irse from chlorin. The operation lssts alittle..

more than l2 hoursn The melt is then diluted With 1Water, tle excess of lime Lis-neutralized with sulturic scid end the camphene formed is distilled oil Witlrstearn. From the remaining solution the Whole 'of the lime is precipitated with sulfuric acid, the Filtered acid solution is saturated with carbonate of l zincsnd the lactate of zinc Obtained by crystallization from the concentrated solution.

Example-Lil. 60() parts 'of lime Water prepared from 'parts of lime src stirred with 345 thics partly solid aste are added 345- parts oi pinene liydrocllorid. The operation is conducted in the seine Way asabovo.v A test of tile oil is taken from the autocls'v'e 1parts* of potete or rice starch and to the and distilled over with steam; the campl'iene is Wholl vtree from clilorinss soon' ostile liquid 'stilled over, when brought onv a, gauze oi' copper 'Wire into the fdarn'oof s Bunsen burner, no longer shows a green colors-' -tion of the sme. v v n l, y

Irlthe examples. given thc-limo cian o'i'A course be' replaced it desired bystrontiilrill oxidor barium Oxid and tire poteteV or rice .starch by their soluble conversion products suoli as soluble starch, dextri'n, starch si or mixtures thereof. p Further the 'co tration can be varied Within-wide limits The invention consists substantiellgr yin heating pinene'. lijfdrocliloridV et relativelyiiigli 'temperatues end under pressure wit alkslies in the presence of higher alcohols or carboli drates, or in similarly heating the pinene l'xydroclilorid with calcium,r strontium 4or "bariuml oxid after having brought the above mentioned earth alkalies into soluble form by Ineens of the higher alcohols or carbolifdrates.

l\ow what l'claim and desire to Letters lPstentA is the following: l

1. The process of manufacturing ceinpliene which consists in hosting, under pressure, pinene hydroclilorid together with alkalies and organic bodies of the fatty series, that contain more than one hydroxykgroup, stirring the mixture, and distillinggoi the Acsmphene with steam.

lf/The process of rnsnuiacturing campnene which consists in nesting, under pressure, pineue liylroclilorid together with silraliesy secure by dnd earbolshydrates; stirringthe mixture and distilling ofi' the cemphene with steam.

steanL y 4. The proeess of manufacturing'cemphene which consists in heating, under pressure nudi nt elevated temperatures, pinene hydroehlorid together with earth nlkelies and carbohydrates, stirring the"riixtu1e, sind.L distillingnf the reerrphene with stesm.V

5. The process of inenufrtcturing camphene which consists 1n heating, under pressure and et elevated temperatures, pinene hydre-l ehiorid together with linie water and. sugar, stirring the mixture, and distiliing' ofi the camphene with steam.

In testimony, thet I claim the foregoing as 'my invention, I have signed my name in resence of two Witnesses, this irst day 0f'- une, 1907. @TTG CHARLES BILLETER.

Witnesses: l e A MELCHIOR BNIGER, GEORGE WAGNER. 

